Obatobies



.40 a After se Rearmed-Jan. 14, who

* UNITED-STA TEs PATENT 'o -FIon] mm; w. names, or rmannrrnn, rnunsnvam, assmnoa "ro Amao'r'r m? ona'ronnzs. or; some: cmcaeo, rumors, aconromrron or more racemes or mnircnm A mcunroomurtn or e-m'rno-onrno-cmor. 'nm

' rnomrc'ir rumor" a I The object of my-present invention, in re search laboratory work,- has been to produce .a mercu derivative of 4-nitro-ortho-cresol,-

never be ore obtained; and which is specific.- 5 ally a mercury derivative of 4-nitro orthocresol, as distinguished"from the mercuri derivative of v 3-nitro-ortho-cresol which forms the subject matter of my Patent N o.

I 1,630,072, dated May 24, 1927, the latter b'e-.

o ing a crystalline product,fwhile my present new pro, not is an amorphous powder. Both of them ossess superior ermicidal properties and 'ence give valuable-them utic eff fectsiwhen such a-medic' al reme y is indi- 1 The inves'ti ations of Otto N. Witt, E. 'Notting, and E. randmougin, ublished in the Berichte der Dents, Chem. 'esellschaftpvolume 23,' 1890, pa c3635, and also of 0. Michel 2e and E. Gran mougin, published in the Berichte Deutschen Chemischen- Gesellschaft, 26, III, 1893, I a e 2349, show that 4-nitro-ortho-cresol is i cult to obtain pure. A considerable amount of impurity called by the above a'uthor nitro-ind'azol is ordinarily obtained. In order to omit the troublesome complete removal of the impurity nitroindazol, I found a procedure y 1 ich the 4-nitro-ortho-cresol is mercurated, while '3 some impurity of nitro-indazol'is present in it. I observed that a mixture ofmercury derivatives can be separated, based on the property that the mercury derivative of 4- nitro-ortho-cresol forms soluble salts with al- ,kali metal hydroxides, in which group is to be included as customary, ammonium h" droxide. I

The mercury derivative of nitro-indazol is "insoluble in a solution of the same reagent.

rating the two mercury deriva-- t ves in t is way, the desired. mercury compound of4- 'tro-ortho-cresol can then be regained from he alkali metal salt solution by acidifying with acetic acid and precipitating' out the compound" orderto make this -process practicable, it is .necessaryto prepare 'the 4-nitro-ortho-cresol in such a way as to avoid the formation of the' nitro-indazol-im purity in too large amounts.' While the process of of l-mtro-ortho-cresol has 155 ki ograms of ori inal Ill'o. 1,554,213, datedifleptember 28, 1 925, Serial llo. ceases, filed July 9, 1m.

Application for reissue med August 7,192 8. Serial llo. 884,289.

been amply described inthe literature, the, followin method is preferable to the process describe in the literature; v 1

Preparation of i-nitro-orthoto luidine u v Sixty-seven kilograms of concentrated sul-' phuric acid are cooled to 0 C. while the acid is being stirred by a mechanical stirrer, to it are ad ed in lo stream 6.1 kilograms of orthmtoluidine and .the temperature'isnot allowed to. rise over 10 C. After all the toluidine has been added f the mixture is cooled to '2 C. To this is added, drop by drop, a nitrating mixture of 3,6 kilograms of nitric acid and 4 kilo ms of sulphuric acid. While nitrating, t e temperature should not, rise above 1 C. When all the nitrating mixture has been added, allow the mixture to be mixed for one-half hour at about 03 C. .This is then clystallized b Pouring the mixture in 180 poun s of cracke ice. Permit it to crystallize for 12 hours. Filter and wash several times with'iee cold water; About 40 liters plewater are used for washing the quantit (obtained. 7 1 p hec'rystalline precipitate, which is orthonitro-toluidine'sulphate is dissolved in '80- liters of boiling water and cooled to 70 0., and 40% sodium hydroxide solution is added until slightly alkaline to litmus paper. Now {cool to 15 C. and filter the recipitate formed, which is 4-I1ltI0-Ol'th0rt0ll1ldill8, wash,

with .cold water until free of sulphates and dry it at ordinary,temperature.

Preparatiqn of crude 4-1tit7'0 07th0-0T680Z 3.2 kilograms of 4-nitro-toluidine are dissolved in a very hot solution obtained by mixing about 36 liters of water with 6.4 liters of concentrated sulphuric acid.- Diazotize-hot (about 90 to C.) stirring rapidly and jeetinglive steam, by adding gradually and slowl in a continuous stream a solution of sodium nitrate in 10 liters of water.

After all. the sodium nitrate solution has been added; the injection of and rapid stirring continues for about-one-half hour. The total volume ofsthe resulting 1i uid is now about liters. N it'ro-i'ndazol 1S so'formed 100 1i ui containing 4-nitro-ortho-creso Land w ich has been separated from th'e' nitroindazol as-muc'h as po ble, is-cooled, whereupon yellow crystals-are obtained; The c stallization isjcompleted upoIr-stan or 12 hours. The'drystals are filtered'o and washed with 40 liters ofcold water and then in the air without; application of heat.

1 of l-aitro-oflho-crewl compound; 1

' '110 gms. of 4-nitro o rth o,-cresol containin some nitro-indazol not completely remove 1 is dissolved in a mixturepf 4,000 cc. hot water and .100 cc. of 40% sodium hydroxide solution. To this is added in a slow stream 220 gms. of mercuric acetate, whichh'as been dissolved in 1,500 cc. boiling .water, conta: a amount,'say 10 cc. lacial acetic acld.

This is stirred mec. anieall and kept,

. for two 2: orty per cent sodium hydroxide lution is then. added drop by drop for the purpose. of neutralizing the acetic acid present. At thispoint'a heavy precipitate is at'a.te m erature close .to 100 foamed; Thisjpreci itateof mercury .com-

pounds consisting o a mixture of the niercuryg derivative of i-nitro-ortho-cresol and merc iryderivative of nitro-indazol 1s filjtered out, while the mixture is yet hot. The

product is washed with about 5 liters of boil mg water; In order to separte the mercury der of items-creel from hot mercury derivativeof nitro-indazolthe above precipitate is extracted several times by means of hot aqueoussolution of alkali 5 C.) using altogether a proximately 10 liters of water, containing a ut 250 combined extracts containing the mercury derivative of 4nitro-ortho-cresol is cooled to 169 'A small amount of a precipitate-rep- ;resenting an unidentified imipurit is formed coolin and is filtered o A v lotion is "en acidified with acetic acid it shows .a neutral reaction tested on litmus paper. A precipitate of mercury compound of -4-nitro-ortho'-cresol thus iormed u n standi is then filtered .ofi washed thorou h.- lywith ot water, methylTalcohol and-ct 81" andr-then dried on a steambath. The result- 4? mathod of in grodnctis a-brownish yellowpowder in 8051 la in water but soluble indilute aqueous alkali metal hzdroirides, insoluble methyl alcohol and et er.- I The following structural I 1. ss? um ydmte or 250 8 conipoun'd of i-nitr -ortho-cresol, ..whic' comprises dissolving 4-nitro-ortho-cresol in a hot a ueues 'solution'oi an alkali metal .hydroxi sandireac .T e clear so:-

idine with 'sulp while th em irical formula of the compound with ether and dried in vacuo. It is a reddish brown powderwhich is soli ible' in water,

slightly solublein. methyl alcohol, and insoluble in ether. As an example 'of one of the" alkali metal salts, the sodium salt is obtained by dissolving the mercury compound of 4-nitro-ortho-cresol in a quantit of hotwater to which, sodium-hydroxide as been added. The solution is poured into meth l product precipitated by t e alcohol and the addition of ether. The precipitate is fil-v teredofl and washed with ether and 'driedin vacuo. It is a reddish brown powder which issoluble in water, slightly soluble inmethyl alcohol and insoluble 1n ether.- L

I clalm as my invention:

-is soluble'ina dilute aqueoussolution of an alkali metal h drate.

1. As a.ne w composition of"matter,"a mer- 2. The met 0d of preparing a mereuri '4 compound of. 4-nitro-.ortho-ciesol, comprises dissolving. 4-nitro-ortho-cresol in ueous solution of vanyalkali metal hydroxi e and reactin on ithesol'ution so formed witha hot aci mercuric acetate solutionand neutralizing acid present by an alkali to precipitate the product.

3. The method of reparing a mereug.

on the solution s6 formed with a hot .aci mercuric acetate-solution, neutralizing -acid present b an al.-

kali-to precipitate the product an purify:

ifijthe product by dissolving it 'in an aque- 0 solution of an. alkali and precipitating the purified product b neutrahzingtheso;

lution with acetic .aci andseparating the roduct'.

compound of 4-nitro-ortho-cresol,, which compr ses reacting in the cold on ortho-toluxture and crystallizingifo'ut ortlio-nitroig-n i tro-ortho-toluidine diazotizing the lat-' preparing a mercury uric acid, nitrating the erm i IFQW X'WR 'W alumin -1m has, and con-vert' the lat v .ter compoun" by alkali'metal hy ate into:

or com und, hot an forming 4nitro-ortho-cresc and precipitating nitro-indazol;

separa the solution 'preci itating4-ni trd-ort li garsol by c lin p g, reacting on 4 nitro-ortho-cresol in an ueous alkali metal hydrate solution with a ot acid mercuric acetate solution and purifying the resulting recipitate by dissolving out the mercur 5 erivative of 4-nitro-ortho-cresol with an a kali solution and neutralizing the separated solution with acetic acid to precipitate the purified product.

5. The method of preparing a mercu compound of 4-nitro-ortho-cresol, whic comprises dissolving 4-nitro-ortho-cresol in a hot aqueous solution of sodium hydroxide and reacting on'the solution so formed with a hot acid mercuric acetate solution and mu vtralizin acid present by sodium hydroxide to precipitate the product. GEORGE WIRAIZISS;

CERTIFICATE or CORRECTION.

Relaane Patent No. l7,'563. Granted January 14, 1930, to

csoncn w. runztss.

It ia ,hereby certified that error appears in the printed specification of the above numbered patent requiring correction aa follows: Page 1, lines 94 and 96, for "nitrate" read nitrite; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 9th day of February, A. D; 1932.

a M. J. Mm. (Seal) Acting Conlniasioner of Patenta.

nitro-ortho-cresol in an ueous alkali metal hydrate solution with a ot acid mercuric acetate solution and purifying the resulting recipitate by dissolving out the mercur 5 erivative of 4-nitro-ortho-cresol with an a kali solution and neutralizing the separated solution with acetic acid to precipitate the purified product.

5. The method of preparing a mercu compound of 4-nitro-ortho-cresol, whic comprises dissolving 4-nitro-ortho-cresol in a hot aqueous solution of sodium hydroxide and reacting on'the solution so formed with a hot acid mercuric acetate solution and mu vtralizin acid present by sodium hydroxide to precipitate the product. GEORGE WIRAIZISS;

CERTIFICATE or CORRECTION.

Relaane Patent No. l7,'563. Granted January 14, 1930, to

csoncn w. runztss.

It ia ,hereby certified that error appears in the printed specification of the above numbered patent requiring correction aa follows: Page 1, lines 94 and 96, for "nitrate" read nitrite; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 9th day of February, A. D; 1932.

a M. J. Mm. (Seal) Acting Conlniasioner of Patenta. 

